CN106807935A - A kind of activation method of the gold nano grain protected by organic ligand - Google Patents
A kind of activation method of the gold nano grain protected by organic ligand Download PDFInfo
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- CN106807935A CN106807935A CN201510862385.7A CN201510862385A CN106807935A CN 106807935 A CN106807935 A CN 106807935A CN 201510862385 A CN201510862385 A CN 201510862385A CN 106807935 A CN106807935 A CN 106807935A
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- 239000010931 gold Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 25
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 17
- 239000013110 organic ligand Substances 0.000 title claims abstract description 11
- 230000004913 activation Effects 0.000 title claims description 16
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims 2
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000011943 nanocatalyst Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 235000013339 cereals Nutrition 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910004042 HAuCl4 Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910014201 BMIMBF4 Inorganic materials 0.000 description 2
- DILSSABZPPUWAZ-UHFFFAOYSA-N benzene;ethanethiol Chemical compound CCS.C1=CC=CC=C1 DILSSABZPPUWAZ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- -1 dichloromethane Alkane Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical class CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
Abstract
The gold nano grain protected by organic ligand is activated with the ionic liquid containing imidazole salts, we are with Au herein25(SR)18As a example by explanation.Such with ionic liquid treat gold nano catalyst due to more preferable flame resistance, fixedness, high chemical stability and heat endurance, hypotoxicity the features such as and have broad application prospects.The method is broadly divided into two steps：(1) first it is synthesis Au25(SR)18Cluster；(2) attempt activating Au with different ionic liquids25(SR)18The organic thiol ligand on surface.Reaction condition of the present invention is gentle and simple and easy to apply, with economic and practical, the advantage of high conversion rate.
Description
Technical field
The invention belongs to technical field of nano material, gold nano grain is activated protected by organic ligand is related generally to
Plant new method.
Background technology
Noble metal nanometer material as metal nano material an important component, because it is only by noble metal
Special physicochemical properties organically combine with the property of nano material, chemical catalysis, the energy,
The field such as electronics and biology has obtained more and more extensive attention.Nano particle synthesizing process there has also been nearly ten years
Certain development, wherein liquid phase synthesizing method have become one of most important method.I.e. with certain templating
Compound and noble metal precursor are reduced by specific reducing agent, under the stabilization and protection of template compound,
So that precious metal ion is gradually reduced to noble metal nano particles.
For now, the method for the gold nano grain that activation is protected by organic ligand also needs to continue to explore.Than
When such as removing part by way of heating and aoxidizing, the size and pattern of particle can be changed, so as to influence it to urge
Change activity.Therefore, this kind of method is not particularly suited for removing the mercaptan part on gold atom cluster surface.Recently, as one
Traditional organic solvent is planted, ionic liquid obtains extensive concern due to its unique performance.Therefore, Wo Mentong
Cross and grope, discovery is had by being added with the ionic liquid of imidazole salts and can be activated under the conditions of comparatively gentle
The gold nano grain of machine ligand protection.So, the invention method of ionic liquid.The method has
Reaction condition is gentle, economic and practical, the features such as high conversion rate.
The content of the invention
The one kind for the gold nano grain protected by organic ligand is activated it is an object of the invention to provide a kind of ionic liquid
New method.
The purpose of the present invention is achieved in the following ways：
A kind of method of the gold nano grain that ionic liquid activation for being added with imidazole salts is protected by organic ligand, specifically
Including following experimental procedure：
(1) with HAuCl4·4H2O is reaction raw materials, is placed in the three neck round bottom flask of 50ml, is dissolved in
In a certain amount of Tetrahydrofuran System, ammonium bromide and tetraoctyl ammonium bromide is added, stir certain hour, added appropriate
Benzene ethyl mercaptan, it is disposable to add reducing agent sodium borohydride (NaBH after 30 minutes4) be dissolved in 4mL frozen water
The sodium borohydride solution of formation, reaction can obtain for three hours, be washed with methyl alcohol and n-hexane, use dichloromethane
Alkane (DCM) dissolving removal insoluble matter, volatilize dichloromethane, obtains Au25(SR)18。
(2) Au of synthesis in 0.5mg steps (1) is weighed25(SR)18Nano-cluster is dissolved in following three kinds of solution：
(1) 2mL dichloromethane solutions；(2) 2mL dichloromethane, relative to Au25(SR)18Nano-cluster 5
The BMIMBF of times molar equivalent4Mixed solution；(3) 2mL dichloromethane, relative to Au25(SR)18
5 times of BMIMBF of molar equivalent of nano-cluster4With relative to Au25(SR)180.30-0.50 of nano-cluster
MM K2CO3Mixed solution, is stirred at room temperature 4 hours.
(3) by TiO2Powder pours into the Au dissolved by dichloromethane25(SR)18In cluster, in vacuum drying chamber
In at 150 DEG C dry 1 hour.
(4) Au of synthesis in 100mg steps (3) is weighed25(SR)18/TiO2(load capacity is 1wt%) and carbon
Sour potassium is added in round-bottomed flask, adds the ethanol of 1mL and relative to Au25(SR)18/TiO25 times of nano-cluster
In following four kinds of ionic liquids of molar equivalent：(1)BMIM·Cl；(2)BMIM·Br；(3)BMIM·PF6；
(4)BMIM·BF4So that mixture is in nitrogen atmosphere in 18 hours of stirring at 90 DEG C.Then
Sample is separated with centrifuge, and ethanol is removed with Rotary Evaporators, then with 2mL extracted by ether crude product three times.
1. activation method described in, it is characterised in that：By gold nano grain be soaked in organic solvent, imidazole salts from
In the mixed solution of sub- liquid and alkali.
2. activation method described in, it is characterised in that：In mixed solution the amount of organic solvent be 2mL, imidazole salts from
The amount of sub- liquid is Au25(SR)185 times of molar equivalents of nano-cluster, the amount of alkali is relative to Au25(SR)18Receive
0.30-0.50 mMs of rice cluster.
2nd, the activation method, it is characterised in that：Soak time is 2-5 hour.
3rd, the activation method, it is characterised in that：Control immersion reaction is carried out at 20-30 DEG C of normal temperature.
Beneficial effect of the present invention is：
(1) process reactant in reaction system of the invention with ionic liquid has more preferable resistance to combustion compared with usual vehicle
Property, fixedness, high chemical stability and heat endurance, hypotoxicity, high ionic conductivity and electrochemistry wide
Window.
(2) imidazolium ionic liquid is added in reaction system of the invention can greatly improve the conversion ratio of reactant.
(3) present invention is simple and convenient with the method that ionic liquid activates the gold nanoclusters protected by organic ligand, it is easy to
Purifying.
Brief description of the drawings
Fig. 1 is gold nano catalyst transmission electron microscope picture prepared by embodiment 2.
Fig. 2 is that the solution of embodiment 3 (1), (2) and (3) activates Au25(SR)18Ultraviolet-ray visible absorbing afterwards
Spectrogram.
Fig. 3 is that the solution of embodiment 3 (1), (2) and (3) activates Au25(SR)18(being dissolved in dichloromethane) it
Cation mode mass spectrogram afterwards.
Fig. 4 is the Au at room temperature of embodiment 425(SR)18/TiO2Nano-cluster BMIMBF4And K2CO3(it is dissolved in
The mixed solvent of ethanol/water) treatment after transmission electron microscope figure.
Specific embodiment
Below in conjunction with the accompanying drawings and specific implementation case come the present invention is described in further detail.
Embodiment 1：Au25(SR)18Synthesis
With 60mgHAuCl4·4H2O is reaction raw materials, is placed in the three neck round bottom flask of 50ml, is dissolved in
In the Tetrahydrofuran System of 15mL, add relative to HAuCl4·4H2O1.16 times of four n-octyl bromides of molar equivalent
Change ammonium 92mg, stir 30min, add relative to HAuCl4·4H2The O5 times of μ L of the benzene ethyl mercaptan of molar equivalent 97,
It is disposable to add reducing agent 55mg sodium borohydrides (NaBH after 30 minutes4) it is dissolved in the boron formed in 4mL frozen water
Sodium hydride solution, reaction can obtain for three hours, be washed with methyl alcohol and n-hexane, with dichloromethane (DCM)
Dissolving removal insoluble matter, volatilize dichloromethane, obtains Au25(SR)18。
Embodiment 2：Control following steps synthesis Au25(SR)18/TiO2
By 100mg TiO2Powder pours into the 1mgAu dissolved by 5mL dichloromethane25(SR)18In cluster,
In dry 1 hour at 150 DEG C in vacuum drying chamber.
If Fig. 1 is gold nano catalyst transmission electron microscope picture prepared by embodiment 2.It is prepared as seen from the figure
Au25(SR)18Nanocluster size is uniform, and its diameter is about 1.3nm.
Embodiment 3：Activation Au25(SR)18Nano-cluster
Weigh the Au of 0.5mg25(SR)18, it is dissolved separately in following three kinds of solution：(1) 2mL dichloromethanes
Alkane solution；(2) 2mL dichloromethane, relative to Au25(SR)185 times of BMIMBF of molar equivalent of nano-cluster4
Mixed solution；(3) 2mL dichloromethane, relative to Au25(SR)185 times of molar equivalents of nano-cluster
BMIM·BF4With relative to Au25(SR)18The K of 0.30-0.50 mM of nano-cluster2CO3Mixed solution,
4 hours are stirred at room temperature.
If Fig. 2 is that the solution of embodiment 3 (1), (2) and (3) activates Au25(SR)18Ultraviolet-visible afterwards
Abosrption spectrogram.As seen from the figure, the weakened at nano-cluster peak after being processed by solution (3), this can
Au can be illustrated25(SR)18There is the change in electronics/structure after the treatment in nano-cluster.
If Fig. 3 is that the solution of embodiment 3 (1), (2) and (3) activates Au25(SR)18(being dissolved in dichloromethane)
Cation mode mass spectrogram afterwards.As seen from the figure, nano-cluster after being processed with solution (2) and (3)
The intensity at peak becomes strong, and two groups of position consistencies at peak.
Embodiment 4：Activation Au25(SR)18/TiO2Nanocluster catalyst
Weigh the Au synthesized in 100mg embodiments 225(SR)18/TiO2(load capacity is 1wt%) and potassium carbonate add
Enter in round-bottomed flask, add the ethanol of 1mL and relative to Au25(SR)18/TiO25 times of molar equivalents of nano-cluster
Following four kinds of ionic liquids in：(1)BMIM·Cl；(2)BMIM·Br；(3)BMIM·PF6；(4)
BMIM·BF4So that mixture is in nitrogen atmosphere in 18 hours of stirring at 90 DEG C.Then sample with from
Scheming is separated, and ethanol is removed with Rotary Evaporators, then with 2mL extracted by ether crude product three times.
If Fig. 4 is the Au at room temperature of embodiment 425(SR)18/TiO2Nano-cluster BMIMBF4And K2CO3It is (molten
In the mixed solvent of ethanol/water) treatment after transmission electron microscope figure.TiO as seen from the figure2On surface
The Au of load25(SR)18The diameter of nano-cluster about in 1.4nm, with unsupported Au25(SR)18Nanocluster size
Substantially it is consistent.
Claims (6)
1. it is a kind of by organic ligand protect gold nano grain activation method, gold nano grain is to be protected by organic ligand
The nanocluster of shield, it is characterised in that：Gold nano grain is soaked in the ionic liquid of organic solvent, imidazole salts
In the mixed solution of body and alkali.
2. activation method according to claim 1, it is characterised in that：The amount of organic solvent is in mixed solution
2mL, the amount of imidazolium ionic liquid is 5 times of molar equivalents of nanocluster, the amount of alkali be relative to
Au25(SR)180.30-0.50 mM of nano-cluster.
3. activation method according to claim 1, it is characterised in that：Soak time is 2-5 hour.
4. activation method according to claim 1, it is characterised in that：Control immersion reaction is in 20-30 DEG C of normal temperature
Under carry out.
5. activation method according to claim 1 and 2, it is characterised in that：The ionic liquid of imidazole salts is
BMIM·BF4, BMIMCl or BMIMPF6In one or two or more kinds；Alkali is K2CO3、Na2CO3
Or NaHCO3In one or two or more kinds；Organic solvent be dichloromethane, toluene or acetone in one kind or
More than two kinds.
6. activation method according to claim 1, it is characterised in that：The nanocluster protected by organic ligand
It is Au-PVP, Au-C2H、Aun(SR)m(SR can be SC2H4Ph, 2- naphthyl mercaptan or Buddha's warrior attendant alkanethiol etc.
In one or two or more kinds, n=25, m=18；N=144, m=60；One kind in n=38, m=24 etc. or
More than two kinds) or Au11(PPh3)7Cl3In one or two or more kinds.
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| CN109420774A (en) * | 2017-08-28 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of preparation of the controllable AgAu alloy nanocluster of atom number, size |
| CN109746430A (en) * | 2017-11-01 | 2019-05-14 | 中国科学院大连化学物理研究所 | A kind of Au23Nano-cluster is converted to Au21The method of nano-cluster |
| CN110115997A (en) * | 2018-02-07 | 2019-08-13 | 中国科学院大连化学物理研究所 | A method of processing gold atom cluster surface organic ligands |
| CN110883341A (en) * | 2018-09-11 | 2020-03-17 | 清华大学 | Preparation method of gold nanoclusters |
| CN112237945A (en) * | 2019-07-18 | 2021-01-19 | 中国科学院大连化学物理研究所 | Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination |
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Cited By (8)
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| CN109420774A (en) * | 2017-08-28 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of preparation of the controllable AgAu alloy nanocluster of atom number, size |
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| CN110115997B (en) * | 2018-02-07 | 2020-11-27 | 中国科学院大连化学物理研究所 | Method for treating organic ligand on surface of gold cluster |
| CN110883341A (en) * | 2018-09-11 | 2020-03-17 | 清华大学 | Preparation method of gold nanoclusters |
| CN110883341B (en) * | 2018-09-11 | 2021-03-30 | 清华大学 | Preparation method of gold nanoclusters |
| CN112237945A (en) * | 2019-07-18 | 2021-01-19 | 中国科学院大连化学物理研究所 | Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination |
| CN112237945B (en) * | 2019-07-18 | 2022-04-08 | 中国科学院大连化学物理研究所 | Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination |
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